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CN-121991122-A - Phosphoric acid ester derivative containing acryloyl and preparation method and application thereof

CN121991122ACN 121991122 ACN121991122 ACN 121991122ACN-121991122-A

Abstract

The invention discloses a phosphate derivative containing an acryloyl group, a preparation method and application thereof, wherein the phosphate derivative has a structure shown in a general formula (I), R1 is a phosphorus-containing functional group and can be selected from a structure (II), (III) or (IV), R2-R6 are C1-C6 alkyl, cycloalkyl or hydrogen, m is 1-4, and X is O, S or N element. The compound has an acryl active functional group and a phosphate flame retardant group, can participate in a free radical copolymerization reaction, realizes intrinsic flame retardance, and solves the problems that the traditional additive flame retardant is easy to migrate, uneven in dispersion and affects transparency. The invention also provides a preparation method based on the micro-channel continuous flow reaction, which is suitable for industrial continuous production by precisely controlling the reaction temperature, pressure and residence time and obviously improving the reaction yield and purity.

Inventors

  • CAO ZHENHU

Assignees

  • 宁波谱多琟克科技发展有限责任公司

Dates

Publication Date
20260508
Application Date
20260116

Claims (10)

  1. 1. An acryl-containing phosphate derivative characterized by having a structure represented by the following general formula (I): (I); Wherein R1 is a phosphorus-containing functional group having the following structural features (II), (III) or (IV): (II)、 (III)、 (IV); Wherein R2, R3, R4, R5 and R6 are the same or different straight-chain or branched-chain alkyl groups with 1-6 carbon atoms, or are cycloalkyl groups, or are hydrogen atoms; m is an integer of 1 to 4; x is O, S or N, wherein when X is N, methyl, ethyl, propyl or isopropyl is connected to N.
  2. 2. The method for preparing an acryl-containing phosphate derivative according to claim 1, wherein the phosphate derivative is synthesized using a micro-channel continuous flow reaction system including a micro-mixer and a micro-channel reactor.
  3. 3. The method for producing an acryl-containing phosphate derivative according to claim 2, wherein, When R1 is a structure (II) and X is an O element, reacting an acrylic acid derivative with a chlorophosphate dialkoxy ester derivative in a micro-channel reactor to obtain a phosphate ester derivative with a structure (I); When R1 is a structure (II) and X is an S element, dialkoxy phosphoryl chloride and sodium sulfide are reacted in a micro-channel reactor to generate an intermediate, and then the intermediate and an acryloyl chloride derivative are reacted in a micro-channel to obtain a phosphate derivative with the structure (I); when R1 is a structure (II) and X is an element N, the acryloyl chloride derivative and dialkoxy phosphoramide are reacted in a micro-channel reactor to obtain the phosphate derivative with the structure (I).
  4. 4. The method for producing an acryl-containing phosphate derivative according to claim 2, wherein when R1 is the structure (III), the acryl chloride derivative is reacted with a trialkyl phosphite in a microchannel reactor to obtain a phosphate derivative having the structure (I).
  5. 5. The method for producing an acryl-containing phosphate derivative according to claim 2, wherein when R1 is the structure (IV) and X is O, S or N, the acryl chloride derivative is reacted with an alkyl dialkoxyphosphonate derivative having O, S or N as a terminal group in a microchannel reactor to obtain a phosphate derivative having the structure (I).
  6. 6. The method for producing an acryl-containing phosphate derivative according to claim 3, wherein, When R1 is a structure (II) and X is an O element, the reaction temperature is-5-35 ℃, the pressure is 0-2 MPa, and the residence time is 1 s-20 min; When R1 is a structure (II) and X is an element N, the reaction temperature is-5-65 ℃, the pressure is 0-1 MPa, and the residence time is 1 s-30 min.
  7. 7. The method for producing an acryl-containing phosphate derivative according to claim 4, wherein when R1 is the structure (III), the reaction temperature is-5 to 35 ℃, the pressure is 0 to 2MPa, and the residence time is 1s to 20min.
  8. 8. The method for producing an acryl-containing phosphate derivative according to claim 5, wherein when R1 is the structure (IV) and X is O, S elements, the reaction temperature is-5 to 80 ℃, the pressure is 0 to 3MPa, and the residence time is 1s to 20min.
  9. 9. The method for producing an acryl-containing phosphate derivative according to claim 5, wherein when R1 is the structure (IV) and X is the element N, dialkoxyalkylamine and acrylic ester are added to the microchannel reactor, and a polymerization inhibitor and a catalyst are added to react at a temperature of 50 to 200℃under a pressure of 0 to 2MPa for a residence time of 1s to 30min.
  10. 10. The use of the acryl-containing phosphate derivative according to claim 1, wherein the phosphate derivative is used as a reactive flame retardant monomer to participate in radical copolymerization of an acrylate, styrene, methacrylate, vinyl acetate, unsaturated polyester matrix containing an olefin functional group.

Description

Phosphoric acid ester derivative containing acryloyl and preparation method and application thereof Technical Field The invention relates to the technical field of high-molecular flame-retardant materials, in particular to a phosphate derivative containing an acryloyl group, and a preparation method and application thereof. Background Conventional polymer materials (particularly those involving radical polymerization) are often used as substrates for optical articles because of their excellent transparency. Meanwhile, compared with the common inorganic material, the high polymer material has the advantages of light weight, safety, easy cutting and installation and the like, and can embody the application advantages of the high polymer material especially in buildings and high-rise buildings. However, the polymer materials have many problems in the practical use process, such as low surface hardness, poor wind-resistant pressure difference, poor heat resistance, weak fire resistance and the like, and the problems severely limit the application range and the use efficiency of the polymer materials. Therefore, various modification researches such as abrasion resistance, heat resistance, flame retardance and the like are carried out on the high polymer material, and development and application researches on the transparent flame retardant high polymer material are carried out. The flame retardant modification method commonly used at present mainly comprises the steps of physically blending an additive flame retardant (the flame retardant does not participate in the reaction with the polymer), such as halogen-based, phosphorus-based, nitrogen-based flame retardants and the like. Although the flame retardant has a certain flame retardant effect, the following problems exist: 1. Poor compatibility with a matrix, and partial migration or precipitation can occur in the long-term use process, so that the flame retardant property is reduced with time; 2. the transparency, mechanical property and thermal stability of the material are affected; 3. The addition amount is large, and the processing performance is poor; 4. some flame retardants (e.g., halogen systems) present environmental and health risks. In order to improve the binding force of the flame retardant and the polymer matrix, the reactive flame retardant is a research hot spot. The flame retardant is introduced into a polymer chain in a chemical bonding mode, so that intrinsic flame retardance is realized. However, the existing reactive phosphate flame retardant often has the problems of severe heat release, more side reactions, low yield, difficult control of the reaction process and the like in the synthesis process, and the industrial application of the existing reactive phosphate flame retardant is restricted. Aiming at the problems, the invention provides a novel phosphate derivative containing acryl and a micro-channel continuous flow preparation method thereof, which realize efficient, safe and controllable synthesis, are suitable for various free radical polymerization systems, and realize both intrinsic flame retardance and high performance of materials. Disclosure of Invention In order to solve the problem that the physical properties of polymers are reduced due to uneven dispersion and easy migration and precipitation when the conventional additive flame retardant is used, the invention provides the phosphate derivative containing the acryloyl, and the preparation method and application thereof. In order to achieve the above purpose, the present invention adopts the following technical scheme: The present invention provides an acryl-containing phosphate derivative (an alkoxyphosphate of acrylic acid having a reactive functional group) having the following structural characteristics: (I); Wherein R1 is a phosphorus-containing functional group having the following structural features (II), (III) or (IV): (II) ; (III); (IV); Wherein R2, R3, R4, R5 and R6 are same or different straight-chain or branched-chain alkyl groups with 1-6 carbon atoms, or cycloalkyl groups, or hydrogen atoms; m is an integer of 1 to 4; X is O, S or N element, wherein N is hydrogen or substituted methyl, ethyl, propyl or isopropyl. The flame retardant properties of the phosphate derivatives are generally better than (III) for (II) and better than (IV). The phosphate derivative has the advantages that the acryloyl in the molecular structure provides free radical reactivity, the phosphate structure provides flame retardant property, and the phosphate derivative are connected through stable chemical bonds, so that the structure is not damaged in the polymerization process. The invention covers a class of compounds, wherein the compounds with high melting point and the compounds with low melting point are included, and the invention has wide application scenes. The compound of the invention can be added in the bulk polymerization process to participate in the copolymerization react